US3548049A - Process for spinning polyvinyl chloride fibers - Google Patents

Process for spinning polyvinyl chloride fibers Download PDF

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Publication number
US3548049A
US3548049A US638177A US3548049DA US3548049A US 3548049 A US3548049 A US 3548049A US 638177 A US638177 A US 638177A US 3548049D A US3548049D A US 3548049DA US 3548049 A US3548049 A US 3548049A
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United States
Prior art keywords
polyvinyl chloride
fibers
drawn
fiber
shrinkage
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Expired - Lifetime
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US638177A
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English (en)
Inventor
Claude Ledoux
Albert De Vries
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Produits Chimiques Pechiney Saint Gobain
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Produits Chimiques Pechiney Saint Gobain
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/10—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polyvinyl chloride or polyvinylidene chloride

Definitions

  • This invention relates to the manufacture of polyvinyl chloride in elongated shapes of uniform section, which had not heretofore been accomplished.
  • Polyvinyl chloride fibers can be made by this process, are of substantial importance, and this invention will be related in its application to their manufacture, it being understood that the process is equally applicable to the manufacture of other shapes the thickness of which is minimum compared to length, for instance ribbons, pellicles, plates.
  • Polyvinyl chloride has been made in shaped sizes of limited length by pressing in a mold but not in sizes of limitless length as by extrusion or other continuous production.
  • limitless is meant to distinguish between objects all the dimensions of which are fixed as made, compared to those of at least one intermediate dimension.
  • Microphoto 1 shows a polyvinyl fiber made from solution in accordance with the prior art
  • Microphoto 2 shows a polyvinyl fiber, at the same enlargement as microphoto 1, which was made in accordance with the present invention.
  • polyvinyl chloride in an elongated shape having an indeterminate dimension and a minimum section, the section of which is substantially uniform, and by a method of making a resinous composition from the class consisting of polyvinyl chloride and its copolymers, and their mixtures 3,548,049 Patented Dec. 15, 1970 with compatible and previously incompatible resins into elongated shapes of minimum section which comprises flowing a stream of polyvinyl chloride in the absence of solvents and diluents toward shaping means, and homogenizing the part of the stream adjacent the shaping means, heating that part rapidly into the range of about C. about to 220 C. thereby making it hot and plastic, shaping the hot, plastic resin in the shaping means drawing and cooling it, the heating, shaping, drawing and cooling of, the homogeneous resin being limited to a time on the order of a few seconds to tens of seconds.
  • the new fibers can be extruded, drawn, and made to rigid specifications of uniformity not previously attainable, even to the manufacture of rigorously exact transverse dimensions.
  • Comparison of the two microphotos furnishes an estimate of the comparative value of the new and the old fibers.
  • the fibers are made from a melt of the resin without the addition of solvent, being extruded from a spinnerette, for example, and drawn as they issue.
  • polyvinyl chloride are useful in the process, e.g. those polymerized hot, those polymerized cold; all its copolymers, e.g. polyvinyl chloride polyvinylidene chloride, polyvinyl chloride acrylic nitrile; super chlorinated polyvinyl chloride; grafted polyvinyl chloride; and those in which the comonomer is ethylenic or acrylic.
  • Particles of different polymers e.g. polyvinyl chloride and polyvinylidene chloride can be rapidly homogenized and heated and extruded together, producing useful fibers of coordinate properties.
  • the process is of extreme rapidity, the completion of homogenization, extrusion drawing and the start of cooling being accomplished in less than a minute.
  • the polyvinyl chloride fllows in a stream toward the spinnerette, the stream is homogenized just before the spinnerette by the most vigorous working, which may itself impart a material rise in temperature, is heated to melting temperature either just before the spinnerette, or in or before the die of the spinnerette itself, and is cooled by air or in a liquid. Before it is cooled it may be subjected to drawing. The whole operation will take less than a minute and in many cases only from a few seconds to a few tens of seconds.
  • the temperatures employed will vary according to the quality (e.g. viscosity and mol weight) of the resin.
  • An exemplary polyvinyl chloride was homogenized, melted, extruded, drawn, and cooled in fifteen seconds at a maximum temp. of 180 C. which was attained only for a few seconds.
  • the standard extrusion apparatus is useful, for instance spinnerets, usually with the addition of means to heat the spinnerette and the zones immediately adjacent to it through which the homogenized resin flows, to the temp. between 150 and 220 C. most useful with the particular resin.
  • the fiber takes a shape closely corresponding to the shape of the extrusion orifice, e.g. circular, elliptical, lobed, triangular, cruciform. Such shapes could not previously be produced.
  • the invention not only provides for the formation of such articles from polymers and copolymers but form mixtures of different polymers and copolymers, even those previously regarded as incompatible, and makes useful articles from them, for instance from mixtures of vinyl resins with olefinic and acrylic types.
  • EXAMPLE 1 Granules of polyvinyl chloride of viscosity index 80 stabilized with a standard stabilizer flow in a stream toward a. small but powerful homogenizer in which they are homogenized and fiuidified at 180 C.
  • the stream of molten polyvinyl chloride is immediately forced through a spinnerette having 350 holes of 1.5 mm. diameter, the spinnerette being held at 180 C.
  • the passage through the extrusion apparatus took 10-15 seconds and the fibers issuing from it were drawn at 50 m./min.
  • a thermal conditioning zone was provided at the discharge part of the spinnerette which permitted the drawing to be completed before the fibers were cooled to set temperature. Ordinary drawing and winding apparatus was used. Microscopic examination showed orientation, a diameter of 105 microns, and a value of 122 deniers. The section was uniformly circular. The following characteristics were determined:
  • a powder of mixed grains of polyvinyl chloride and polypropylene to 10%) was supplied to the mixer and forced through the spinnerette.
  • the speed of the extruded fibers measured after drawing was 150 meters per minute.
  • the spinnerette had 200 rectangular holes 3 mm. on one side and 1.2 mm. on the other. Total time of heating approached 25 seconds.
  • the temperature employed approached 220 C.
  • the fibers were of uniform section, had a weight ratio of 35 deniers, had high and uniform luster, and retained their uniformity when drawn. Tests revealed the following properties:
  • EXAMPLE 5 The apparatus used was that which is described in the previous US. application a copolymer of vinylchloride and propylene (-5) was extruded through a spinnerette having 150 holes of three lobes which produced a fiber having three longitudinal channels. Each hole had a 0.55 sq. millimeter of orifice. The fibers extruded were of the exact size and shape of the holes. Compression, melting and extrusion were almost simultaneous (temperature attained 150 C. and did not attain 220 C.). Cooling was in the air after drawing. Drawing was between 80 and C. The part of the stream of copolymer subjected to heating was only that portion nearest the extrusion means.
  • EXAMPLE 7 Using conditions similar either to Example 6 and a miX- ture of 95% by weight polyvinyl chloride and 5% polymethylmethacrylate produced fibers having the qualities:
  • Fibers have been spun according to the novel process from polyvinyl chloride of index of viscosity 80. Each fiber had a weight ratio of 4.1 deniers after having been drawn at 950 m./min.
  • a same fabric made with fibers of equal sizes but prepared according to the prior art has the following characteristics:
  • the fibers are useful in all types of fabrics, rugs, curtains, cloth and in all situations where thermoplastic fibers are useful.
  • the fibers are the first of polyvinyl chloride base which are uniform in their useful properties, for instance having homogeneous composition, uniformity of size and strength, resistance to chemicals such as halogenated hydrocarbon solvents, and uniformity of thermal response.
  • the homogeneity and uniformity are superior to anything previously known.
  • homogeneity of composition may be lacking in appearance, two or more phases being visible under the microscope, but homogeneity of properties is still present even in cases where the resins used were previously deemed too incompatible to be used together.
  • shape total superiority is established because the resins can be extruded in the exact shape desired, which was totally impossible with solvent systems of manufacture. Exact reproducibility of any fiber in composition, appearance, and shape is achieved by this invention, a fact which initself vastly extends the use of polyvinyl chloride polymers and mixtures.
  • the new fibers may be flexible or stifi, thick or thin, solid or tubular, depending on the construction of the extrusion orifice.
  • the shapes may be pellicular, e.g. like ribbons, and of all other shapes of equal or different transverse and vertical dimensions.
  • Modifiers may be included during the mixing, such as are normally used with such compositions, for instance plasticizers and fillers. Inclusion of materials such as solvents capable of creating voids, is to be avoided except when, for reasons pertaining to appearance, voids are desired in the fiber, in which case loss of novel properties is to be expected.
  • novel fibers when extruded as pure resins are normally transparent and of high luster.
  • Delustering agents heretofore satisfactory with polyvinyl chloride may be included before or after extrusion.
  • novelty of attractive appearance follows, sometimes accompanied by internal reflection and refraction of light.
  • a method of making homopolymeric polyvinyl chloride into elongated shapes of minimum and uniform section which comprises continuously moving solid polyvinyl chloride in the absence of solvents and diluents toward shaping means, homogenizing the part of the stream immediately adjacent the shaping means by vigorously working the said part while heating that part rapidly until it is hot and plastic, shaping the hot, plastic polyvinyl chloride in the said shaping means at similar plasticizing temperature, and cooling the shaped polyvinyl chloride after it leaves the shaping means, the heating, shaping, and cooling of the polyvinyl chloride being limited to less than a minute and being generally on the order of a few seconds to a few tens of seconds.
  • a method of shaping homopolymeric vinyl chloride free of solvents and diluents into shapes, including ribbons, fibers, pellicles, bristles and thin plates, of strictly regular cross-section, homogeneous in structure, resistant to chlorinated organic solvents and to heat, highly trar1s parent and of high polish which comprises heating the polyvinyl chloride to plastic temperature, subjecting it to centripetal shearing and mixing at a plastic temperature suitable to extrusion, extruding it in the desired shape, drawing it, and cooling the shaped resinous compositions obtained, the entire process from said heating to the completion of cooling taking less than a minute.
  • the method of making homopolymeric polyvinyl chloride fiber which comprises moving a stream of particulate polyvinyl chloride free of solvents and diluents toward extrusion means heated to extrusion temperature, heating the part of the stream contiguous to the extrusion means rapidly to extrusion temperature while working and homogenizing it by centripetal shearing action, extruding it, and cooling it, the heating, extruding, and cooling requiring less than a minute.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
US638177A 1966-04-27 1967-04-24 Process for spinning polyvinyl chloride fibers Expired - Lifetime US3548049A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR59303A FR1487357A (fr) 1966-04-27 1966-04-27 Fibres essentiellement régulière obtenues à partir de compositions polymères ou copolymères à base de chlorure de vinyle
FR97350A FR92396E (fr) 1966-04-27 1967-03-03 Filbres essentiellement régulières obtenues à partir de compositions polymères ou copolymères à base de chlorure de vinyle

Publications (1)

Publication Number Publication Date
US3548049A true US3548049A (en) 1970-12-15

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US638177A Expired - Lifetime US3548049A (en) 1966-04-27 1967-04-24 Process for spinning polyvinyl chloride fibers

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US (1) US3548049A (enExample)
BE (1) BE697543A (enExample)
DE (1) DE1669512A1 (enExample)
FR (2) FR1487357A (enExample)
GB (1) GB1136320A (enExample)
NL (1) NL6705947A (enExample)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2513839A1 (de) * 1975-03-27 1976-10-14 Wacker Chemie Gmbh Verfahren zur herstellung von folien aus vinylchlorid-vinylacetat-copolymerisaten

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3009208A (en) * 1957-03-02 1961-11-21 Bemberg Ag Process for production of tubular blown foils of polyvinyl chloride interpolymers
US3097991A (en) * 1957-06-10 1963-07-16 Union Carbide Corp Synthetic fibrous products
US3099067A (en) * 1957-09-13 1963-07-30 Union Carbide Corp Plastic fibers
FR1369199A (fr) * 1963-09-13 1964-08-07 Kurashiki Rayon Co Moulage de polymères
FR1377244A (fr) * 1963-12-19 1964-10-31 Monofilamentos Y Derivados Perfectionnement au procédé de fabrication de filaments à partir de polymères
FR1385171A (fr) * 1963-03-12 1965-01-08 Kurashiki Rayon Co Procédé de filage par fusion de substances mixtes
FR1411097A (fr) * 1963-07-22 1965-09-17 Kurashiki Rayon Co Procédé de fabrication d'articles façonnés à partir de fibres filées mixtes
US3234313A (en) * 1961-07-03 1966-02-08 Union Carbide Corp Thermoplastic films and process for preparing same
US3303253A (en) * 1964-03-04 1967-02-07 Owens Illinois Inc Method and apparatus for extruding thermoplastic material
US3372219A (en) * 1963-02-12 1968-03-05 Rhovyl Sa Synthetic fibres based upon polyvinyl chloride
US3382305A (en) * 1954-10-29 1968-05-07 Du Pont Process for preparing oriented microfibers
US3411180A (en) * 1965-05-19 1968-11-19 Pechiney Saint Gobain Plastic extrusion machine
US3444269A (en) * 1965-08-23 1969-05-13 Monsanto Co Polyblends comprising a vinyl chloride graft copolymer,a styrene-methyl methacrylate-butadiene graft copolymer and a vinyl polymer

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3382305A (en) * 1954-10-29 1968-05-07 Du Pont Process for preparing oriented microfibers
US3009208A (en) * 1957-03-02 1961-11-21 Bemberg Ag Process for production of tubular blown foils of polyvinyl chloride interpolymers
US3097991A (en) * 1957-06-10 1963-07-16 Union Carbide Corp Synthetic fibrous products
US3099067A (en) * 1957-09-13 1963-07-30 Union Carbide Corp Plastic fibers
US3234313A (en) * 1961-07-03 1966-02-08 Union Carbide Corp Thermoplastic films and process for preparing same
US3372219A (en) * 1963-02-12 1968-03-05 Rhovyl Sa Synthetic fibres based upon polyvinyl chloride
FR1385171A (fr) * 1963-03-12 1965-01-08 Kurashiki Rayon Co Procédé de filage par fusion de substances mixtes
FR1411097A (fr) * 1963-07-22 1965-09-17 Kurashiki Rayon Co Procédé de fabrication d'articles façonnés à partir de fibres filées mixtes
FR1369199A (fr) * 1963-09-13 1964-08-07 Kurashiki Rayon Co Moulage de polymères
FR1377244A (fr) * 1963-12-19 1964-10-31 Monofilamentos Y Derivados Perfectionnement au procédé de fabrication de filaments à partir de polymères
US3303253A (en) * 1964-03-04 1967-02-07 Owens Illinois Inc Method and apparatus for extruding thermoplastic material
US3411180A (en) * 1965-05-19 1968-11-19 Pechiney Saint Gobain Plastic extrusion machine
US3444269A (en) * 1965-08-23 1969-05-13 Monsanto Co Polyblends comprising a vinyl chloride graft copolymer,a styrene-methyl methacrylate-butadiene graft copolymer and a vinyl polymer

Also Published As

Publication number Publication date
DE1669512A1 (de) 1970-07-23
FR92396E (fr) 1968-10-31
FR1487357A (fr) 1967-07-07
BE697543A (enExample) 1967-10-25
NL6705947A (enExample) 1967-10-30
GB1136320A (en) 1968-12-11

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